Iron-bearing clays are ubiquitously distributed as mineral dusts in the atmosphere. Bromophenols were reported as the major products from thermal decomposition of the widely used brominated flame retardants (BFRs). However, little information is available for the reactivity of iron associated with mineral dusts to interact with the atmospheric bromophenols and the subsequent toxic effects. Herein, three common clay minerals (montmorillonite, illite and kaolinite) were used to simulate mineral dusts, and the reactions with gaseous 2-bromophenol were systematically investigated under environmentally relevant atmospheric conditions. Our results demonstrate that structural Fe(III) in montmorillonite and Fe(III) from iron oxide in illite mediated the dimerization of 2-bromophenol to form hydroxylated polybrominated biphenyl and hydroxylated polybrominated diphenyl ether. The surface reaction is favored to occur at moisture environment, since water molecules formed complex with 2-bromophenol and the reaction intermediates via hydrogen bond to significantly lower the reaction energy and promote the dimerization reaction. More importantly, the formed dioxin-like products on clay mineral dust increased the toxicity of the particles to A549 lung cell by decreasing cell survival and damaging cellular membrane and proteins. The results of this study indicate that not only mineral dust itself but also the associated surface reaction should be fully considered to accurately evaluate the toxic effect of mineral dust on human health.

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

Sealcoat is an emulsified coating product applied to asphalt to protect against surface weathering. Sealcoat products contain coal-tar (CT) or petroleum-derived residues and are a recognized source of polycyclic aromatic hydrocarbons (PAHs) in urban areas. Although the toxicity of urban runoff from CT-sealed asphalt is established, chemical characterization has focused more on PAHs and alkylated derivatives and less on polar transformation products. In this study, solid-phase extraction (SPE) was used to concentrate dissolved (<0.2 μm) species in runoff collected from asphalt surfaces sealed with CT pitch or steam-cracked petroleum (SCP) residues. CT-sealed surfaces released a 20-fold greater concentration of SPE-extractable compounds in runoff compared to SCP-sealed surfaces. Representative compounds were sorted into four groups: nitrogen heterocycles (azaarenes) and other oxygen- and sulfur-containing species (N HET); hydroxylated N heterocycles (hydroxylated N HET); the nonionic surfactant 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD); and styrene-acrylonitrile polymer byproducts (SAN Trimer). Species concentrations and weathering-related disappearance behavior differed among the four subgroups. While hydroxylated N HET concentrations decreased by 94% in runoff from CT-sealed surfaces 60 h after sealcoat application, SAN Trimer concentrations in CT and SCP runoff increased over time as polymerization progressed, illustrating the complex changes the chemicals in sealcoat undergo as it cures under environmentally-relevant conditions. Overall, this study shows that urban runoff collected from CT-sealed and SCP-sealed asphalt surfaces is a potential source of water-soluble contaminants with unknown long-term ecotoxicological effects to aquatic systems.

Lead (Pb) and polycyclic aromatic hydrocarbon (PAH) exposure is positively associated with cardiovascular disease (CVD), and the possible potential mechanism may be caused by damage to the endothelium by modulation of inflammatory processes. No comprehensive research shows co-exposure of Pb and PAH on cardiovascular endothelial inflammation in electronic waste (e-waste) exposed populations. Given this, the aim of this study is to provide evidence for a relationship between Pb and PAH co-exposure and cardiovascular endothelial inflammation, in an e-waste-exposed population, to delineate the link between a potential mechanism for CVD and environmental exposure. We recruited 203 preschool children (3–7 years) were enrolled from Guiyu (e-waste-exposed group, n = 105) and Haojiang (reference group, n = 98). Blood Pb levels and urinary PAH metabolites were measured. Percentages of T cells, CD4⁺ T cells and CD8⁺ T cells, complete blood counts, endothelial inflammation biomarker (serum S100A8/A9), and other inflammatory biomarkers [serum interleukin (IL)-6, IL-12p70, gamma interferon-inducible protein 10 (IP-10)] levels were evaluated. Blood Pb, total urinary hydroxylated PAH (ΣOHPAH), total hydroxynaphthalene (ΣOHNap) and total hydroxyfluorene (ΣOHFlu) levels, S100A8/A9, IL-6, IL-12p70 and IP-10 concentrations, absolute counts of monocytes, neutrophils, and leukocytes, as well as CD4⁺ T cell percentages were significantly higher in exposed children. Elevated blood Pb, urinary 2-hydroxynaphthalene (2-OHNap) and ΣOHFlu levels were associated with higher levels of IL-6, IL-12p70, IP-10, CD4⁺ T cell percentages, neutrophil and monocyte counts. Mediator models indicated that neutrophils exert the significant mediation effect on the relationship between blood Pb levels and S100A8/A9. IL-6 exerts a significant mediation effect on the relationship between blood Pb levels and IP-10, as well as the relationship between urinary ΣOHFlu levels and IP-10. Our results indicate that children with elevated exposure levels of Pb and PAHs have exacerbated vascular endothelial inflammation, which may indicate future CVD risk in e-waste recycling areas.

Once released into the environment, engineered nanomaterials can significantly influence the transformation and fate of organic contaminants. To date, the abilities of composite nanomaterials to catalyze environmentally relevant abiotic transformation reactions of organic contaminants are largely unknown. Herein, we investigated the effects of two nanocomposites – consisting of anatase titanium dioxide (TiO2) with different predominantly exposed crystal facets (i.e., {101} or {001} facets) anchored to hydroxylated multi-walled carbon nanotubes (OH-MWCNT) – on the hydrolysis of 1,1,2,2-tetrachloroethane (TeCA), a common groundwater contaminant, at ambient pH (6, 7 and 8). Both OH-MWCNT/TiO2 nanocomposites were more effective in catalyzing the dehydrochlorination of TeCA than the respective component materials (i.e., bare OH-MWCNT and bare TiO2). Moreover, the synergistic effect of the two components was evident, in that the incorporation of OH-MWCNT increased the TeCA adsorption capacity of the nanocomposites, significantly enhancing the catalytic effect of the deprotonated hydroxyl and carboxyl groups on nanocomposite surfaces, which served as the main catalytic sites for TeCA hydrolysis. The findings may have important implications for the understanding of the environmental implications of composite nanomaterials and may shed light on the design of high-performance nanocomposites for enhanced contaminant removal.

Increasing attention has been attracted in developing new technologies to remove chlorofene (CF) and dichlorofene (DCF), which were active agents in antimicrobials for general cleaning and disinfecting. This study investigated the significant influences of bicarbonate (HCO3−) on the degradation of CF and DCF in the Cu(II)-mediated Fenton-like system Cu2+/H2O2. Our results indicate that HCO3− may play a dual role to act 1) as a ligand to stabilize Cu(II), forming soluble [CuII(HCO3−)(S)]+ species to catalyze H2O2 producing hydroxyl radical (OH) and superoxide ion (O2−) and 2) as a OH scavenger. Furthermore, the reaction kinetics, mechanisms, and intermediates of CF and DCF were assessed. The apparent rate constants of CF and DCF were enhanced by a factor of 8.5 and 5.5, respectively, in the presence of HCO3− at the optimized concentration of 4 mM. Based on the intermediate identification and frontier electron densities (FEDs) calculations, the associated reaction pathways were tentatively proposed, including C–C scission, single or multiple hydroxylation, and coupling reaction. In addition, significant reduction in the aquatic toxicity of CF and DCF was observed after treatment with Cu2+/H2O2–HCO3- system, evaluated by Ecological Structure Activity Relationships (ECOSAR) program. These findings provide new insights into Cu(II)-mediated reactions to better understand the environmental fate of organic contaminants in carbonate-rich waters.

Airborne lower-chlorinated PCBs are vulnerable to metabolization to PCB sulfates through further sulfation of the hydroxylated metabolites (OH-PCBs). However, studies on the toxic effects and mechanisms of PCB sulfates are still very limited. Here, we investigated for the first time the potential endocrine disruption effects of PCB sulfates through estrogen-related receptor γ (ERRγ) in comparison with their OH-PCBs precursors and PCB parent compounds. The binding affinity of thirteen PCBs/OH-PCBs/PCB sulfates was measured by using fluorescence competitive binding assays based on fluorescence polarization (FP). All of the tested chemicals could bind to ERRγ with the Kd (dissociation constant) values ranging from not available (NA) to 3.2 μM 4′–OH–PCB 12 showed the highest binding affinity with Kd value of 3.2 μM, which was comparable to that of a synthetic ERRγ agonist GSK4716. The effects of the thirteen chemicals on the ERRγ transcriptional activity were determined by using the luciferase reporter gene assay. We found the PCBs/OH-PCBs/PCB sulfates acted as agonists for ERRγ, with the lowest observed effective concentration reaching 3 μM. The binding affinity and agonistic activity of PCBs towards ERRγ were both enhanced after hydroxylation, while further sulfation of OH-PCBs decreased the activity instead. Molecular docking simulation showed that OH-PCBs had lower binding energy than the corresponding PCBs and PCB sulfates, indicating that OH-PCBs had higher binding affinity theoretically. In addition, OH-PCBs could form hydrogen bonds with amino acids Glu316 and Arg247 while PCBs and PCB sulfates could not, which might be the main factor impacting the binding affinity and agonistic activity. Overall, ERRγ is a novel target for lower-chlorinated PCBs and their metabolites.

Interest in the presence of pharmaceutically active compounds in the aquatic environment has been growing for over 20 years, yet very few studies deal with the metabolism of pharmaceuticals in marine organisms. In this study, the bioaccumulation under short-term conditions and metabolism of diclofenac were investigated. Mytilus trossulus was used as a representative of the Baltic benthic fauna. The mussels were exposed to diclofenac at a concentration of 133.33 μg/L for five days, following a five-day depuration phase. The highest concentration of diclofenac (7.79 μg/g dw) in tissues was determined on day 3. Subsequently, the concentration of diclofenac in tissues decreased rapidly to 0.86 μg/g dw on day 5. After five days of depuration, the concentration of diclofenac was 0.21 μg/g dw. Hydroxylated diclofenac metabolites were found both in tissues of mussels and water. This study shows that M. trossulus has the potential to accumulate diclofenac and metabolize it to 4-OH and 5-OH diclofenac.

1,3,5-Tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione (TDBP-TAZTO) is an emerging brominated flame retardant which is widely used in several plastic materials (electric and electronic equipment, musical instruments, automotive components). However, until today, no photochemical studies as well as the identification of possible phototransformation products (PTPs) were described in literature. Therefore, in this study, UV-(C) and simulated sunlight irradiation experiments were performed to investigate the photolytic degradation of TDBP-TAZTO and to identify relevant PTPs for the first time. The UV-(C) irradiation experiments show that the photolysis reaction follows a first-order kinetic model. Based on this, the photolysis rate constant k as well as the half-life time t₁/₂ were calculated to be k = (41 ± 5 × 10⁻³) min⁻¹ and t₁/₂ = (17 ± 2) min. In comparison, a minor degradation of TDBP-TAZTO and no formed phototransformation products were obtained under simulated sunlight. In order to clarify the photochemical behavior, different chemicals were added to investigate the influence on indirect photolysis: (i) H₂O₂ for generation of hydroxyl radicals and (ii) two quenchers (2-propanol, sodium azide) for scavenging oxygen species which were formed during the irradiation experiments. Herein, nine previously unknown PTPs of TDBP-TAZTO were detected under UV-(C) irradiation and identified by HPLC-(HR)MS. As a result, debromination, hydroxylation, and dehydrobromination reactions could be presumed as the main degradation pathways by high-resolution mass spectrometry. The direct as well as the OH radical-induced indirect photolysis were observed. Graphical abstract .

Solutions with 0.65 mM of the antituberculosis drug isoniazid (INH) in 0.050 M Na₂SO₄ at pH 3.0 were treated by electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) processes using a cell with a BDD anode and a carbon-PTFE air-diffusion cathode. The influence of current density on degradation, mineralization rate, and current efficiency has been thoroughly evaluated in EF. The effect of the metallic catalyst (Fe²⁺ or Fe³⁺) and the formation of products like short-chain linear aliphatic carboxylic acids were assessed in PEF. Two consecutive pseudo-first-order kinetic regions were found using Fe²⁺ as catalyst. In the first region, at short time, the drug was rapidly oxidized by ●OH, whereas in the second region, at longer time, a resulting Fe(III)-INH complex was much more slowly removed by oxidants. INH disappeared completely at 300 min by EF, attaining 88 and 94% mineralization at 66.6 and 100 mA cm⁻², respectively. Isonicotinamide and its hydroxylated derivative were identified as aromatic products of INH by GC-MS and oxalic, oxamic, and formic acids were quantified by ion-exclusion HPLC. The PEF treatment of a real wastewater polluted with the drug led to slower INH and TOC abatements because of the parallel destruction of its natural organic matter content.